CN108262073A - A kind of application of metal organic framework load phosphotungstic acid catalyst, preparation method and Synthesis of Adipic Acid Catalyzed - Google Patents
A kind of application of metal organic framework load phosphotungstic acid catalyst, preparation method and Synthesis of Adipic Acid Catalyzed Download PDFInfo
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- CN108262073A CN108262073A CN201810034571.5A CN201810034571A CN108262073A CN 108262073 A CN108262073 A CN 108262073A CN 201810034571 A CN201810034571 A CN 201810034571A CN 108262073 A CN108262073 A CN 108262073A
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- organic framework
- metal organic
- acid
- phosphotungstic acid
- catalyst
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 48
- 239000001361 adipic acid Substances 0.000 title claims abstract description 41
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 41
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000013207 UiO-66 Substances 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003504 terephthalic acids Chemical class 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 42
- 238000004064 recycling Methods 0.000 abstract description 9
- 230000002194 synthesizing effect Effects 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000011017 operating method Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012924 metal-organic framework composite Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- -1 adipic acid Hexanone Chemical compound 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
- B01J2523/48—Zirconium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of metal organic framework load phosphotungstic acid catalyst, including carrier and the active component being carried on carrier：Wherein, the carrier is metal organic framework, and the active component is phosphotungstic acid, and the invention also discloses the applications of the preparation method and Synthesis of Adipic Acid Catalyzed of metal organic framework load phosphotungstic acid catalyst.Catalyst prepared by the present invention maintains the characteristics of carrier high-specific surface area, and environmentally friendly, reaction condition is mild, and efficiently and stability is good, and catalyst can realize recycling.
Description
Technical field
The invention belongs to chemical industry synthesis fields, are related to the metal organic framework composite catalyst of synthesizing adipic acid, the present invention
More particularly to the application of a kind of metal organic framework load phosphotungstic acid catalyst, preparation method and Synthesis of Adipic Acid Catalyzed.
Background technology
Adipic acid is also known as adipic acid, is a kind of important basic chemical industry raw material and organic synthesis intermediate, is mainly used as synthesizing
The raw materials for production of fiber (such as nylon -66), polyester foam and synthetic resin, it can also be used to produce ester plasticizer, lubrication
Oil additive, food additives and textile treating agent etc..Traditional Production Processes of Adipic Acid mainly uses nitric acid oxidation method, with
The concentrated nitric acid oxidation cyclohexanol and cyclohexanone (KA oil) of strong oxidizing property obtain adipic acid, production process severe corrosion to equipment, together
When can also generate a large amount of high-concentration waste acid solution body and N2The oxides of nitrogen gas such as O, environmental pollution are serious.Therefore, one is developed
The green cleaning of kind production process, environment amenable adipic acid synthetic method have important environment protection significance and industrial value.
One of direction studied at present is to replace nitric acid using cleaning oxidizer.Hydrogen peroxide is a kind of ideal cleaning oxygen
Agent, unique by-product of its own reaction is water.With hydrogen peroxide as oxidant, needing under the effect of the catalyst could be by ring
Hexanol or cyclohexanone are converted into adipic acid, and the catalyst used is mostly Tungstenic compound, such as tungstates and phosphotungstic acid.Directly with tungsten
When hydrochlorate or phosphomolybdic acid catalyst, due to the presence of " false liquid phase " behavior, cause recycling for catalyst extremely difficult, produce
Object impurities are more.
Patent CN102614920 is described the immobilized catalysis on silica or polystyrene resin carrier of tungstates
Agent preparation method, and by the catalyst for catalysis oxidation cyclohexene synthesizing adipic acid, catalyst, which realizes, to be recycled, but urge
The preparation process of agent is more complicated, and the patent is not directed to and carrys out synthesizing adipic acid as raw material using cyclohexanol or cyclohexanone.
Also it has been reported that and makees catalyst (Industrial Catalysis, 2009,17 (7), 46-48 using immobilized phosphotungstic acids such as aluminium oxide, silica；West
Pacify engineering college journal, 2017,31 (1), 36-40), it can realize the recycling of catalyst, but the ratio of these conventional carriers
Surface area is smaller, and active component phosphotungstic acid cannot effectively disperse in carrier surface, easily reunite in reaction process, causes to urge
The stability of agent is poor.
Metal organic framework (metal-organic frameworks) be by metal ion or metal cluster unit with it is organic
Ligand has the porous material of periodical multidimensional network structure by one kind that coordination is self-assembly of, and has very high ratio
Surface area and adjustable pore passage structure.For this field, exploitation is a kind of to utilize the catalyst that metal organic framework is carrier
There is long-range meaning to adipic acid preparation field to synthesizing adipic acid.
Invention content
For the prior art there are problem, the purpose of the present invention is to provide a kind of catalyst for catalyzing and synthesizing oneself two
Acid, and the catalyst efficient stable.
For achieving the above object, following technical solution is specifically provided：
A kind of metal organic framework load phosphotungstic acid catalyst, including carrier and the active component being carried on carrier：Its
In, the carrier is metal organic framework, and the active component is phosphotungstic acid.
Further, the mass ratio of the metal organic framework and phosphotungstic acid is 1.5~9:1.
The present invention also provides the preparation methods of the metal organic framework load phosphotungstic acid catalyst, provide following two
Kind：
Method A:Metal organic framework is scattered in hydrophobic solvent to obtain dispersion liquid, under fast stirring into dispersion liquid by
Phosphotungstic acid aqueous solution is added dropwise to, continues stirring 1~10 hour, is filtered, obtained solid is dried in vacuo 6~12 at 100~150 DEG C
Hour is to get metal organic framework load phosphotungstic acid catalyst；
Method B:Organic ligand, zirconium source metal, n,N-Dimethylformamide, phosphotungstic acid are mixed into simultaneously ultrasound 5~30 minutes,
Kept for 12~48 hours, be cooled to room temperature at 100~150 DEG C, centrifuge, sedimentation solid n,N-Dimethylformamide and
Methanol washs successively, and 12~24 hours are finally dried in vacuo at 150~180 DEG C to get metal organic framework load phosphotungstic acid
Catalyst.
Further, in method A, the hydrophobic solvent is n-hexane or normal heptane.
Further, in method A, the metal organic framework is UiO-66 series materials.
Organic ligand described in method B is terephthalic acid (TPA), amino-containing terephthalic acid (TPA), the terephthaldehyde containing nitro
One or more of sour, carboxylic terephthalic acid (TPA), brominated terephthalic acid (TPA) and terephthalic acid (TPA) containing chlorine；The zirconium
Source metal is zirconium chloride or zirconyl nitrate.
Further, n,N-Dimethylformamide described in method B, phosphotungstic acid, organic ligand, zirconium source metal molar ratio be
75~225:0.01~0.06:0.5~2:1.
The present invention further discloses answering for the metal organic framework load phosphotungstic acid catalyst Synthesis of Adipic Acid Catalyzed
With, which is characterized in that the application includes the following steps：By metal organic framework load phosphotungstic acid catalyst, acid ligand, double
Oxygen water and reaction substrate are added in reactor, are heated to 60~110 DEG C after mixing, are stirred to react 2~24 hours.Reaction
After filter while hot, filtrate stands overnight at 0 DEG C, and the white crystal of precipitation is filtered, is washing, dry to get adipic acid
Product, the reaction substrate are cyclohexanol or cyclohexanone.
Further, the acid ligand is one or more of oxalic acid, phosphoric acid and citric acid.
Further, the mass ratio of the metal organic framework load phosphotungstic acid catalyst and reaction substrate for 0.01~
0.60:1, the molar ratio of acid ligand, hydrogen peroxide and reaction substrate is 0~1：3~12：1.
The beneficial effects of the present invention are：Using metal organic framework as carrier in the present invention, using phosphotungstic acid as load group
Conjunction forms catalyst, and discloses two kinds of preparation methods, and catalyst prepared by two methods maintains carrier high-specific surface area
And the characteristics of high stability, method A prepares metal organic framework composite catalyst by Double solvent method, organic using metal
The hydrophilic different and capillarity in skeleton inside and outside, phosphotungstic acid is incorporated in full into the hole of metal organic framework, is formed
Nucleocapsid improves the stability of catalyst；Method B prepares metal organic framework composite material using the hot method of direct solvent and urges
Phosphotungstic acid is encapsulated in the hole of metal organic framework by agent in situ by single step reaction, is formed nucleocapsid, is improved and urge
The stability of agent, two kinds of catalyst preparation process are simple and can be recycled, and product is easily isolated purification, and reaction system need not
Add organic solvent and phase transfer catalyst, the cleaning of production process green.And using the production of this catalyst synthesizing adipic acid
Rate is high, and catalyst can be realized and be recycled.
Description of the drawings
Fig. 1 shows the XRD spectrums of catalyst A, catalyst B and UiO-66
Specific embodiment
The present invention is described further below in conjunction with specific embodiment：
Embodiment 1
(1) preparation of metal organic framework load phosphotungstic acid catalyst
According to method A, 1.6g metal organic framework UiO-66 and 100mL anhydrous n-hexanes are added in into round-bottomed flask, are surpassed
Sound disperses 30min, and 686 μ L (the i.e. metal organic frameworks of phosphotungstic acid aqueous solution of a concentration of 1g/mL are added dropwise under fast stirring
Mass ratio with phosphotungstic acid is 2.3:1), continue to stir 8h, filter, obtained solid is dried in vacuo 10h at 120 DEG C, that is, prepares
Metal organic framework load phosphotungstic acid catalyst is obtained, labeled as catalyst A.
(2) synthesis of adipic acid
0.5g catalyst A, 0.056g oxalic acid (0.62mmol) is added in into round-bottomed flask and 15.9mL mass fractions are
30% hydrogen peroxide (155mmol), adds 3g cyclohexanone (31mmol) after stirring evenly, 8h is stirred to react at 90 DEG C, will
Mixture after reaction filters while hot, and filtrate stands overnight at 0 DEG C, and the white crystal of precipitation is filtered and is washed with a small amount of cold water
It washs, the yield that adipic acid is obtained after dry is 83.56%.
Embodiment 2
For operating procedure with embodiment 1, difference lies in 3.1g cyclohexanol (31mmol) alternate collar is added in during synthesizing adipic acid
Hexanone, the yield for obtaining adipic acid are 72.90%.
Embodiment 3
Operating procedure is 0 difference lies in oxalic acid addition during synthesizing adipic acid, obtains the yield of adipic acid with embodiment 1
It is 61.20%.
Embodiment 4
Operating procedure is 0 difference lies in oxalic acid addition during synthesizing adipic acid, obtains the yield of adipic acid with embodiment 2
It is 54.66%.
Embodiment 5
(1) preparation of metal organic framework load phosphotungstic acid catalyst
According to method B, by 1.6g terephthalic acid (TPA)s (9.6mmol), 2.2g zirconium chlorides (9.4mmol) and 1.12g phosphotungstic acids
(0.39mmol) adds to 60mLN, and dinethylformamide (775mmol), ultrasound 20min, mixed liquor is shifted after mixing
It is static at 120 DEG C to keep for 24 hours into the stainless steel cauldron equipped with polytetrafluoroethylliner liner, reaction postcooling to room temperature, from
Heart separation, sedimentation solid n,N-Dimethylformamide and methanol filter after washing successively, and obtained solid vacuum at 160 DEG C is done
Metal organic framework load phosphotungstic acid catalyst is prepared in dry 16h, labeled as catalyst B.
(2) synthesis of adipic acid
0.5g catalyst B, 0.056g oxalic acid (0.62mmol) is added in into round-bottomed flask and 15.9mL mass fractions are
30% hydrogen peroxide (155mmol), adds 3g cyclohexanone (31mmol) after stirring evenly, 8h is stirred to react at 90 DEG C, will
Mixture after reaction filters while hot, and filtrate stands overnight at 0 DEG C, and the white crystal of precipitation is filtered and is washed with a small amount of cold water
It washs, the yield that adipic acid is obtained after dry is 78.85%.
Embodiment 6
For operating procedure with embodiment 5, difference lies in 3.1g cyclohexanol (31mmol) alternate collar is added in during synthesizing adipic acid
Hexanone, the yield for obtaining adipic acid are 67.54%.
Embodiment 7
The recycling performance evaluation of catalyst A：
Operating procedure difference lies in synthesizing adipic acid after completion of the reaction, will filter urging for gained while hot with embodiment 1
Agent is fully washed with methanol, and 6h is dried in vacuo at 120 DEG C to get to the catalyst of recycling.Utilize the catalyst weight of recycling
The synthetic reaction of multiple adipic acid, operating procedure are recycled to the 5th, the yield for obtaining adipic acid is 76.85% with embodiment 1.
Embodiment 8
The recycling performance evaluation of catalyst B：Operating procedure is with embodiment 5, and difference lies in the anti-of synthesizing adipic acid
Should after, the catalyst for filtering gained while hot with methanol is fully washed, 6h is dried in vacuo at 120 DEG C to get to recycling
Catalyst.The synthetic reaction of adipic acid is repeated using the catalyst of recycling, operating procedure is recycled with embodiment 5 to the 5th
Secondary, the yield for obtaining adipic acid is 73.10%.
Further by catalyst A prepared by embodiment 1 and catalyst B and metal organic framework prepared by embodiment 5
UiO-66 carries out X-ray diffraction analysis, diffracting spectrum as shown in Figure 1 is obtained, as seen from Figure 1, using method A solvent pairs
The catalyst B that the catalyst A and the hot method of method B direct solvents that method is prepared are prepared and pure carrier metal organic backbone
The TuPu method of UiO-66 is consistent, illustrates the variation for not causing UiO-66 crystal framework structures after immobilized phosphotungstic acid；Catalyst A
With do not occur the diffraction maximum of phosphotungstic acid in catalyst B, illustrate that phosphotungstic acid is entered in the hole of metal organic framework, form
Nucleocapsid.
And it can also reflect from Examples 1 to 8, catalyst prepared by two methods maintains carrier high-specific surface area
And the characteristics of high stability, two kinds of catalyst preparation process are simple, and product is easily isolated purification, and reaction system need not add organic
Solvent and phase transfer catalyst, the cleaning of production process green.And, catalysis high using this catalyst synthesizing adipic acid yield
Agent can be realized and be recycled.In addition, during Synthesis of Adipic Acid Catalyzed, whether acid ligand, which adds in, can directly influence adipic acid
Yield.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of metal organic framework load phosphotungstic acid catalyst, which is characterized in that including carrier and the work being carried on carrier
Property component：Wherein, the carrier is metal organic framework, and the active component is phosphotungstic acid.
2. a kind of metal organic framework load phosphotungstic acid catalyst according to claim 1, which is characterized in that the metal has
The mass ratio of machine skeleton and phosphotungstic acid is 1.5~9:1.
3. the preparation method of any one of the claim 1~2 metal organic framework load phosphotungstic acid catalyst, feature exist
In,
Method A:Metal organic framework is scattered in hydrophobic solvent and obtains dispersion liquid, is added dropwise into dispersion liquid under fast stirring
Enter phosphotungstic acid aqueous solution, continue stirring 1~10 hour, filter, it is small that obtained solid is dried in vacuo 6~12 at 100~150 DEG C
When to get metal organic framework load phosphotungstic acid catalyst；
Method B:Organic ligand, zirconium source metal, n,N-Dimethylformamide, phosphotungstic acid are mixed into simultaneously ultrasound 5~30 minutes,
It is kept for 12~48 hours, is cooled to room temperature at 100~150 DEG C, centrifuged, settle solid n,N-Dimethylformamide and first
Alcohol washs successively, is finally dried in vacuo 12~24 hours at 150~180 DEG C and is urged to get metal organic framework load phosphotungstic acid
Agent.
4. the preparation method of metal organic framework load phosphotungstic acid catalyst according to claim 3, which is characterized in that method
In A, the hydrophobic solvent is n-hexane or normal heptane.
5. the preparation method of metal organic framework load phosphotungstic acid catalyst according to claim 3, which is characterized in that method
In A, the metal organic framework is UiO-66 series materials.
6. the preparation method of metal organic framework load phosphotungstic acid catalyst according to claim 3, which is characterized in that method
Organic ligand described in B is terephthalic acid (TPA), amino-containing terephthalic acid (TPA), the terephthalic acid (TPA) containing nitro, carboxylic right
One or more of phthalic acid, brominated terephthalic acid (TPA) and terephthalic acid (TPA) containing chlorine；The zirconium source metal is chlorination
Zirconium or zirconyl nitrate.
7. the preparation method of metal organic framework load phosphotungstic acid catalyst is stated according to claim 3, which is characterized in that method B
Described in N,N-dimethylformamide, phosphotungstic acid, organic ligand, zirconium source metal molar ratio be 75~225:0.01~0.06:
0.5~2:1.
8. the application of any one of the claim 1~2 metal organic framework load phosphotungstic acid catalyst Synthesis of Adipic Acid Catalyzed,
It is characterized in that, the application includes the following steps：By metal organic framework load phosphotungstic acid catalyst, acid ligand, dioxygen
Water and reaction substrate are added in reactor, are heated to 60~110 DEG C after mixing, are stirred to react 2~24 hours.Reaction knot
It is filtered while hot after beam, filtrate stands overnight at 0 DEG C, and the white crystal of precipitation is filtered, is washed, is dry to get adipic acid production
Product, the reaction substrate are cyclohexanol or cyclohexanone.
9. the application of metal organic framework load phosphotungstic acid catalyst Synthesis of Adipic Acid Catalyzed according to claim 8, special
Sign is that the acid ligand is one or more of oxalic acid, phosphoric acid and citric acid.
10. the application of metal organic framework load phosphotungstic acid catalyst Synthesis of Adipic Acid Catalyzed according to claim 8, special
Sign is that the mass ratio of the metal organic framework load phosphotungstic acid catalyst and reaction substrate is 0.01~0.60:1, it is acid
The molar ratio of ligand, hydrogen peroxide and reaction substrate is 0~1：3~12：1.
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